Method for processing silver halide color photographic material

ABSTRACT

A method for processing a silver halide color photographic material containing at least one pyrazoloazole magenta coupler represented by general formula (I), which comprises processing the light-sensitive material, after imagewise exposure, with a color developer containing an aromatic primary amine color developing agent and at least one member selected from among hydrazines and hydrazides represented by general formula (II): ##STR1## wherein R 11  represents a hydrogen atom or a substituent, X represents a hydrogen atom or a group capable of being eliminated by a coupling reaction with an oxidation product of an aromatic primary amine developing agent, Za, Zb and Zc each represents a methine group, a substituted methine group, ═N-- or --NH--, provided that one of the Za-Zb bond and the Zb-Zc bond is a double bond and the other is a single bond and, when Zb-Zc is a carbon-to-carbon double bond, it may be a part of an aromatic ring, and a dimer or higher polymer may be formed at R 11  or X, or, when Za, Zb or Zc represents a substituted methine group, a dimer or higher polymer may be formed at the substituted methine group; ##STR2## wherein R 1 , R 2  and R 3  each independently represents a hydrogen atom, an alkyl group, an aryl group or a meterocyclic group, R 4  represents a hydrogen atom, a hydroxy group, a hydrazino group, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, a carbamoyl group or an amino group, X 1  represents a divalent group, and n represents 0 to 1, provided that, when n is 0, R 4  represents an alkyl group, an aryl group or a heterocyclic group, and that R 3  and R 4  may together form a heterocyclic ring.

FIELD OF THE INVENTION

This invention relates to a method for processing a silver halide colorphotographic material and, more particularly, to a method which isexcellent in processing properties, color-forming properties, and colorfading resistance and, further, provides a color developer havingexcellent stability.

BACKGROUND OF THE INVENTION

Magenta couplers represented by the following general formula (I) areknown from, for example, JP-A No. 59-162548 (The term "JP-A" as usedherein means an "unexamined published Japanese patent application"),JP-A No. 60-43659, JP-A No. 59-171956, JP-A No. 60-172982, and JP-A No.60-33552, and U.S. Pat. No. 3,061,432, and various studies have beenmade thereon due to their excellent hues: ##STR3## wherein R₁₁represents a hydrogen atom or a substituent, X represents a hydrogenatom or a group capable of being eliminated by a coupling reaction withan oxidation product of an aromatic primary amine developing agent, Za,Zb, and Zc each represents a methine group, a substituted methine group,═N-- or --NH--, provided that one of the Za--Zb bond and the Zb--Zc bondis a double bond and the other is a single bond and, when Zb--Zc is acarbon-to-carbon double bond, it may be a part of an aromatic ring, anda dimer or higher polymer may be formed at R₁₁ or X, or, when Za, Zb orZc represents a substituted methine group, a dimer or higher polymer maybe formed at the substituted methine group.

It has been found, however, that magenta couplers of general formula (I)have the defect that, when processed with a conventional colordeveloper, they show poor color-forming properties, a serious variationin photographic properties and, after being processed, are liable tocause magenta stain with time.

As to variation of photographic properties, it has been found thatvariations in the concentration of sulfite ion (conventionally added toa color developer) have a serious influence. Therefore, variouspreservatives or chelating agents have been added to color developers tokeep the above-described concentration of sulfite ion at a constantlevel in a stable fashion. However, effective techniques have not yetbeen discovered. It has then been found that when sulfite ion iseliminated, the concentrations of hydroxylamines or color-developingagents vary so much that there also results a detrimental influence onphotographic properties. Therefore, preservatives for replacing sulfiteion are necessary. However, the addition of triethanolamines describedin U.S. Pat. No. 4,170,478 and poly(ethyleneimines) described in U.S.Pat. No. 4,252,892 have failed to provide sufficient results.

On the other hand, as to formation of magenta stain caused afterprocessing, conventional anti-fading techniques or stain-preventingtechniques (anti-fading techniques include adding various compounds suchas hydroquinone derivatives described in, for example, U.S. Pat. Nos.2,360,290, 2,418,613, 2,675,314, 2,701,197, 2,704,713, 2,728,659,2,732,300, 2,735,765, 2,710,801, and 2,816,028, British Pat. No.1,363,921, and JP-A No. 58-24141, gallic acid derivatives described inU.S. Pat. Nos. 3,457,079 and 3,069,262, p-alkoxyphenols described inU.S. Pat. Nos. 2,735,765, and 3,698,909, JP-B No. 49-20977 (the term"JP-B" as used herein means an "examined Japanese patent publication")and JP-B No. 52-6623, p-hydroxyphenol derivatives described in U.S. Pat.Nos. 3,432,300, 3,573,050, 3,574,627 and 3,764,337, JP-A No. 52-35633,JP-A No. 52-147434 and JP-A No. 52-152225, and bisphenols described inU.S. Pat. No. 3,700,455; and the stain-preventing techniques describedin, for example, JP-A No. 49-11330, JP-A No. 50-57223, JP-A No.56-85747, and JP-B No. 56-8346) have failed to provide sufficientresults.

As is described above, it has been desired to develop a technique ofovercoming the defects of magenta couplers represented by generalformula (I).

SUMMARY OF THE INVENTION

As a result of intensive studies, the inventors have found that theobjects of the present invention can effectively be attained byemploying the following technique. That is, the above-described problemscan be solved by a method for processing a silver halide colorphotographic material, which comprises processing a silver halidelight-sensitive material containing at least one pyrazoloazole typemagenta coupler represented by following general formula (I), afterimagewise exposure, with a color developer containing an aromaticprimary amine color developing agent and at least one member selectedfrom among hydrazines and hydrazides represented by following generalformula (II): ##STR4## wherein R₁₁ represents a hydrogen atom Or asubstituent, X represents a hydrogen atom or a group capable of beingeliminated by a coupling reaction with an oxidation product of anaromatic primary amine developing agent, Za, Zb, and Zc each representsa methine group, a substituted methine group, ═N-- or --NH--, providedthat one of the Za--Zb bond and the Zb--Zc bond is a double bond and theother is a single bond and, when Zb--Zc is a carbon-to-carbon doublebond, it may be a part of an aromatic ring, and a dimer or higherpolymer may be formed at R₁₁ or X, or, when Za, Zb or Zc represents asubstituted methine group, a dimer or higher polymer may be formed atthe substituted methine group; ##STR5## wherein R¹, R² and R³ eachindependently represents a hydrogen atom, an alkyl group, an aryl groupor a heterocyclic group, R⁴ represents a hydrogen atom, hydroxy group, ahydrazino group, an alkyl group, an aryl group, a heterocyclic group, analkoxy group, an aryloxy group, a carbomoyl group or an amino group, X¹represents a divalent group, and n represents 0 or 1, provided that,when n is 0, R⁴ represents an alkyl group, an aryl group or aheterocyclic group, and R³ and R⁴ may together form a heterocyclic ring.

DETAILED DESCRIPTION OF THE INVENTION

Particularly, it was not expected that the above-described defects withthe couplers of general formula (I) could be removed by processing witha color developer containing the compound represented by general formula(II) (that is, at least one member selected from among hydrazines andhydrazides) which does not substantially contain benzyl alcohol.

Magenta couplers represented by general formula (I) are described indetail below.

In general formula (I), the term "polymer" means one which contains twoor more groups represented by general formula (I) per molecule, and thepolymer includes bis derivatives and polymer couplers. The polymercoupler may be a homopolymer composed of only monomers (preferably thosecontaining a vinyl group, which are hereinafter referred to as "vinylmonomers") having the moiety represented by general formula (I) or acopolymer with a non-color forming, ethylenic monomer not coupling withan oxidation product of an aromatic amine developing agent.

The compounds represented by general formula (I) are 5-memberedring/5-membered ring condensation type nitrogen-containing heterocycliccouplers, whose color-forming matrix nucleus shows an aromaticityelectronically equal to naphthalene and has a chemical structure usuallygiven a generic name of azapentalene. Of the couplers represented bygeneral formula (I), preferable couplers are1H-imidazo-(1,2-b)pyrazoles, 1H-pyrazolo(1,5-b)pyrazoles, 1H-pyrazolo(5,1-c)(1,2,4-triazoles, 1H-pyrazolo(1,5-b)(1,2,4)triazoles,1H-pyrazolo(1,5-d)tetrazoles, and 1H-pyrazolo(1,5-a)benzimidazoles,which are respectively represented by the following general formulae(Ia), (Ib), (Ic), (Id), (Ie) and (If). Of these, compounds representedby (Ia), (Ic) and (Id) are particularly preferable, with (Id) being moreparticularly preferable. ##STR6##

In general formulae (Ia) to (If), R₁₂, R₁₃ and R₁₄ each independentlyrepresents a hydrogen atom, a halogen atom, an alkyl group, an arylgroup, a heterocyclic group, a cyano group, an alkoxy group, an aryloxygroup, a heterocyclic oxy group, an acyloxy group, a carbomoyloxy group,a silyloxy group, a sulfonyloxy group, an acylamino group, an anilinogroup, a ureido group, an imido group, a sulfamoylamino group, acarbomoylamino group, an alkylthio group, an arylthio group, aheterocyclic thio group, an alkoxycarbonylamino group, anaryloxycarbonylamino group, a sulfonamido group, a carbomoyl group, anacyl group, a sulfamoyl group, a sulfonyl group, a sulfinyl group, analkoxycarbonyl group, or an aryloxycarbonyl group, and X represents ahydrogen atom, a halogen atom, a carboxy group or a coupling-off groupbound to the carbon atom at the coupling site through an oxygen atom, anitrogen atom or a sulfur atom. Further, R₁₂, R₁₃, R₁₄ or X may be adivalent group to form a bis derivative. When the moiety represented bygeneral formula (Ia) to (If) constitutes a part of a vinyl monomer, R₁₂,R₁₃ or R₁₄ represents a single bond or a linking group through which themoiety represented by general formula (Ia) to (If) is bound to the vinylgroup.

More particularly, R₁₂, R₁₃ and R₁₄ each represents a hydrogen atom, ahalogen atom (for example chlorine or bromine), an alkyl group (forexample, methyl, propyl, i-propyl, t-butyl, trifluoromethyl, tridecyl,3-(2,4-di-tamylphenoxy)propyl, 2-dodecyloxyethyl, 3-phenoxypropyl,2-hexylsulfonyl-ethyl, cyclopentyl or benzyl), an aryl group (forexample, phenyl, 4-t-butylphenyl, 2,4-di-t-amylphenyl,4-tetradecanamidophenyl), a heterocyclic group (for example, 2-furyl,2-thienyl, 2-pyrimidinyl or 2-benzothiazolyl), a cyano group, an alkoxygroup (for example, methoxy, ethoxy, 2-methoxyethoxy,2-dodecyloxyethoxy, 2 -phenoxyethoxy or 2-methanesulfonylethoxy), anaryloxy group (for example, phenoxy, 2-methylphenoxy or4-t-butylphenoxy), a heterocyclic oxy group (for example,2-benzimidazolyloxy), an acyloxy group (for example, acetoxy orhexadecanoyloxy), a carbamoyloxy group (for example,N-phenylcarbamoyloxy or N-ethylcarbomoyloxy), a silyloxy group (forexample, trimethylsilyloxy), a sulfonyloxy group (for example,dodecylsulfonyloxy), an acylamino group (for example, acetamido,benzamido, tetradecanamido, α-(2,4-di-t-amylphenoxy)butylamido,γ-(3-t-butyl-4-hydroxyphenoxy)butylamido orα-{4-(4-hydroxyphenylsulfonyl)phenoxy}decanamido), an anilino group (forexample, phenylamino, 2-chloroanilino, 2-chloro5-tetradecanamidoanilino, 2-chloro-5-dodecyloxycarbonylanilino,N-acetylanilino or2-chloro-5-{α-(3-t-butyl-4-hydroxyphenoxy)dodecanamido}anilino), aureido group (for example, phenylureido, N-butyl-N'-methylureido,methylureido or N,N-dibutylureido), an imido group (for example,N-succinimido, 3-benzylhydantoinyl,4-(2-ethylhexanoylamino)phthalimido), a sulfamoylamino group (forexample, N,N-dipropylsulfamoylamino or N-methyl-N-decylsulfamoylamino),a carbamoylamino group (for example, carbamoylamino, orN,N-dimethylcarbamoylamino), an alkylthio group (for example,methylthio, octylthio, tetradecylthio, 2-phenoxyethylthio,3-phenoxypropylthio, 3-(4-t-butylphenoxy)propylthio), an arylthio group(for example, phenylthio, 2-butoxy-5-t-octylphenylthio,3-pentadecylphenylthio, 2-carboxyphenylthio or4-tetradecanamidophenylthio), a heterocyclic thio group (for example,2-benzothiazolylthio), an alkoxycarbonylamino group (for example,methoxycarbonylamino or tetradecyloxycarbonylamino), anaryloxycarbonylamino group (for example, phenoxycarbonylamino or2,4-di-tert-butylphenoxycarbonylamino), a sulfonamido group (forexample, methanesulfonamido, hexadecanesulfonamido, benzenesulfonamido,p-toluenesulfonamido, octadecanesulfonamido or2-methyloxy-5-t-butylbenzenesulfonamido), a carbamoyl group (forexample, N-ethylcarbamoyl, N,N-dibutylcarbamoyl,(2-dodecyloxyethyl)carbamoyl, N-methyl-N-dodecylcarbamoyl orN-{3-(2,4-di-tert-amylphenoxy)propyl}carbamoyl), an acyl group (forexample, acetyl, (2,4-di-tertamylphenoxy)-acetyl or benzoyl), asulfamoyl group (for example, N-ethylsulfamoyl group,N,N-dipropylsulfamoyl, N-(2-dodecyloxyethyl)-sulfamoyl,N-ethyl-N-dodecylsulfamoyl or N,N-diethylsulfamoyl), a sulfonyl group(for example, methanesulfonyl, octanesulfonyl, benzenesulfonyl ortoluenesulfonyl), a sulfinyl group (for example, octanesulfinyl,dodecylsulfinyl or phenylsulfinyl), an alkoxycarbonyl group (forexample, methoxycarbonyl, butyloxycarbonyl, dodecyloxycarbonyl oroctadecyloxycarbonyl) or an aryloxycarbonyl group (for example,phenyloxycarbonyl or 3-pentadecylphenyloxy-carbonyl).

X represents a hydrogen atom, a halogen atom (for example, chlorine,bromine or iodine), a carboxyl group or a group bound through an oxygenatom (for example, acetoxy, prapanoyloxy, benzoyloxy,2,4-dichlorobenzoyloxy, ethoxyoxaloyloxy, pyruvinyloxy, cinnamoyloxy,phenoxy, cyanophenoxy, 4-methanesulfonamidophenoxy,4-methanesulfonylphenoxy, α-naphthoxy, 3-pentadecylphenoxy,benzyloxycarbonyloxy, ethoxy, 2-cyanoethoxy, benzyloxy, phenethyloxy,2-phenoxyethoxy, 5-phenyltetrazolyloxy, or 2-benzothiazolyloxy), a groupbound through a nitrogen atom (for example, benzenesulfonamido,N-ethyltoluenesulfonamido, heptafluorobutanamido,2,3,4,5,6-pentafluorobenzamido, octanesulfonamido, p-cyanophenylureido,N,N-diethylsulfamoylamino, 1-piperidyl,dimethyl-2,4-dioxo-3-oxazolidinyl, 1-benzyl-ethoxy-3-hydantoinyl,2N-1,1-dioxo-3(2H)-oxo-1,2-benzoisothiazolyl,2-oxo-1,2-dihydro-1-pyridinyl, imidazolyl, pyrazolyl,3,5-diethyl-1,2,4-triazol-1-yl, 5- or 6-bromo-benzotriazol-1-yl,5-methyl-1,2,3,4-triazol-1-yl, benzimidazolyl, 3-benzyl-1-hydantoinyl,1-benzyl-5-hexadecyloxy-3-hydantoinyl, 5-methyl-1-tetrazolyl,4-methoxyphenylazo, 4-pivaloylaminophenylazo,2-hydroxy-4-propanoylphenylazo) or a group bound through a sulfur atom(for example, phenylthio, 2-carboxyphenylthio,2-butoxy-5-t-octylphenylthio, 4-methanesulfonamidophenylthio,2,5-dibutoxyphenylthio, 4-methanesulfonylphenylthio,4-octanesulfonamidophenylthio, 2-butoxyphenylthio,4-dodecyloxyphenylthio,2-(2-hexanesulfonylethyl)-5-tert-octylphenylthio, benzylthio,2-cyanoethylthio, 1-ethoxycarbonyltridecylthio,5-phenyl-2,3,4,5-tetrazolylthio, 2-benzothiazolylthio, 2-dodecylthio,2-dodecylthio-5-thiophenylthio,2-phenyl-3-dodecyl-1,2,4-triazolyl-5-thio).

In the case where R₁₂, R₁₃, R₁₄ or X is a divalent group to form a bisderivative, examples of the divalent group include a substituted orunsubstituted alkylene group (for example, methylene, ethylene,1,10-decylene or --CH₂ CH₂ --O--CH₂ CH₂ --), a substituted orunsubstituted phenylene group (for example, 1,4-phenylene,1,3-phenylene, ##STR7## and --NHCO--R₁₅ --CONH-- (wherein R₁₅ representsa substituted or unsubstituted alkylene or a substituted orunsubstituted phenylene group).

Examples of the linking group represented by R₁₂, R₁₃ and R₁₄ in thecase where the moiety represented by general formula (Ia) to (If)constitutes a part of vinyl monomer include those which are formed bycombining those selected from among an alkylene group (substituted orunsubstituted alkylene group of, for example, methylene, ethylene,1,10-decylene or --CH₂ CH₂ OCH₂ CH₂ --), a phenylene group substitutedor unsubstituted phenylene group of, for example, 1,4-phenylene,1,3-phenylene, ##STR8## --NHCO--, --CONH--, --O--, --OCO-- and anaralkylene group (for example, ##STR9##

Additionally, the vinyl group of the vinyl monomer includes those whichposses a substituent or substituents in addition to those represented bygeneral formulae (Ia) to (If). Preferable substituents are a hydrogenatom, a chlorine atom or a lower alkyl group containing 1 to 4 carbonatoms.

As the non-color forming ethylenic monomers not coupling with anoxidation product of an aromatic primary amine developing agent, thereare illustrated, for example, acrylic acid, α-chloroacrylic acid,alkylacrylic acid (e.g., methacrylic acid), esters or amides of theseacrylic acids (for example, acrylamide, n-butylacrylamide,t-butylacrylamide, diacetoneacrylamide, methacrylamide, methyl acrylate,ethyl acrylate, n-propyl acrylate, n-butyl acrylate, t-butyl acrylate,iso-butyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, laurylacrylate, methyl methacrylate, ethyl methacryllate, n-butyl methacrylateand β-hydroxymethacrylate), methylenedibisacrylamide, vinyl esters (forexample, vinyl acetate, vinyl propionate, and vinyl laurate),acrylonitrile, methacrylonitrile, aromatic vinyl compounds (for example,styrene and its derivatives, vinyltoluene, divinylbenzene,vinylacetophenone and sulfostyrene), itaconic acid, citraconic acid,crotonic acid, vinylidene chloride, vinyl alkyl ethers (for example,vinyl ethyl ether), maleic acid, maleic anhydride, maleic esters,N-vinyl-2-pyrrolidone, N-vinylpyridine and 2- and 4-vinylpyridine. Twoor more of these non-color forming ethylenically unsaturated monomersmay be used in combination.

Examples of the couplers represented by general formulae (Ia) to (If)and processes for synthesizing them are described in the literatureshown below.

Compounds of general formula (Ia) are described in JP-A No. 59-162548,compounds of general formula (Ib) are described in JP-A No. 60-43659,compounds of general formula (Ic) are described in JP-B No. 47-27411,compounds of general formula (Id) are described in JP-A No. 59-171956and JP-A No. 60-172982, compounds of general formula (Ie) are describedin JP-A No. 60-33552, and compounds of general formula (If) aredescribed in U.S. Pat. No. 3,061,432.

High color-forming ballast groups described in, for example, JP-A No.58-42045, JP-A No. 59-214854, JP-A No. 59-177553, JP-A No. 59-177544 andJP-A No. 59-177557 may be substituted with any group of theabove-described compounds of general formulae (Ia) to (If).

Specific examples of pyrazoloazole couplers used in the presentinvention are illustrated below, which, however, are not limitative.##STR10##

These couplers of general formula (I) are generally added to a silverhalide emulsion layer in amounts of 2×10⁻³ mol to 5×10⁻¹ mol, preferably1×10⁻² mol to 5×10⁻¹ mol, per mol of silver in the emulsion layer.

In order to obtain satisfactory properties required for light-sensitivematerials, two or more of the above-described couplers may be usedtogether in one and the same layer, or one and the same compound may ofcourse be added to two or more different layers.

Introduction of the couplers into silver halide emulsion layers may beconducted according to processed described in, for example, U.S. Pat.No. 2,322,027. For example, couplers are dissolved in an alkyl phthalate(for example, dibutyl phthalate or dioctyl phthalate), a phosphoric acidester (for example, diphenyl phosphate, triphenyl phosphate, tricresylphosphate, dioctyl butyl phosphate), a citric acid ester (for example,tributyl acetylcitrate), a benzoic acid ester (for example, octylbenzoate), an alkylamide (for example, diethyllaurylamide), an fattyacid ester (for example, dibutoxyethyl succinate or diethyl azelate), atrimesic acid ester (for example tributyl trimesate) or in an organicsolvent having a boiling point of about 30° C. to about 150° C. (forexample, a lower alkyl acetate such as ethyl acetate or butyl acetate,ethyl propionate, secbutyl alcohol, methyl isobutyl ketone,β-ethoxyethyl acetate or methylcellosolve acetate), then dispersed in ahydrophilic colloid. The above-described high-boiling organic solventand the low-boiling organic solvent may be used as a mixture.

Compounds of general formula (II) to be used in the present invention,that is, hydrazine analogues composed of hydrazines and hydrazides, aredescribed in detail below.

R¹, R² and R³ each independently represents a hydrogen atom, asubstituted or unsubstituted alkyl group (preferably containing 1 to 20carbon atoms; for example, methyl, ethyl, sulfopropyl, carboxybutyl,hydroxyethyl, cyclohexyl, benzyl or phenethyl), a substituted orunsubstituted aryl group (preferably containing 6 to 20 carbon atoms;for example, phenyl, 2,5-dimethoxyphenyl, 4-hydroxyphenyl or2-carboxyphenyl) or a substituted or unsubstituted heterocyclic group(preferably containing 1 to 20 carbon atoms and preferably being a 5- to6-membered ring containing at least one of oxygen, nitrogen and sulfuras hetero atom; for example, pyridin-4-yl or N-acetylpiperidin-4-yl).

R⁴ represents a hydrogen atom, a hydroxy group, a substituted orunsubstituted hydrazino group (for example, hydrazino, methylhydrazinoor phenylhydrazino), a substituted or unsubstituted alkyl group(preferably containing 1 to 20 carbon atoms; for example, methyl, ethyl,sulfopropyl, carboxybutyl, hydroxyethyl, cyclohexyl, benzyl, t-butyl orn-octyl), a substituted or unsubstituted aryl group (preferablycontaining 6 to 20 carbon atoms; for example, phenyl,2,5-dimethoxyphenyl, 4-hydroxyphenyl, 2-carboxyphenyl, 2-carboxyphenylor 4-sulfophenyl), a substituted or unsubstituted heterocyclic group(preferably containing 1 to 20 carbon atoms and being preferably a 5- to6-membered ring containing at least one of oxygen, nitrogen and sulfuras hetero atom; for example, pyridin-4-yl or imidazolyl), a substitutedor unsubstituted alkoxy group (preferably containing 1 to 20 carbonatoms; for example, methoxy, ethoxy, methoxyethoxy, benzyloxy,cyclohexyloxy or octyloxy), a substituted or unsubstituted aryloxy group(preferably containing 6 to 20 carbon atoms; for example, phenoxy,p-methoxyphenoxy, p-carboxyphenyl or p-sulfophenoxy), a substituted orunsubstituted carbamoyl group (preferably containing 1 to 20 carbonatoms; for example, unsubstituted carbamoyl, N,N-diethylcarbamoyl orphenylcarbamoyl), or a substituted or unsubstituted amino group(preferably containing 0 to 20 carbon atoms; for example, amino,hydroxyamino, methylamino, hexylamino, methoxyethylamino,carboxyethylamino, sulfoethylamino, N-phenylamino orp-sulfophenylamino).

As further substituents for R¹, R², R³ and R⁴, a halogen atom (forexample, chlorine or bromine), a hydroxy group, a carboxy group, a sulfogroup, an amino group, an alkoxy group, an amido group, a sulfonamidogroup, a carbamoyl group, a sulfamoyl group, an alkyl group, an arylgroup, an aryloxy group, an alkylthio group, an arylthio group, a nitrogroup, a cyano group, a sulfonyl group or a sulfinyl group arepreferable, and these may further be substituted.

X¹ preferably represents a divalent organic residual group, andspecifically represents, for example, --CO--, --SO₂ -- or ##STR11## nrepresents 0 or 1, provided that, when n is 0, R⁴ represents a groupselected from among a substituted or unsubstituted alkyl, aryl andheterocyclic groups. R¹ and R², and R³ and R⁴ may optionally togetherform a heterocyclic group.

When n=0, at least one of R¹ to R⁴ preferably represents a substitutedor unsubstituted alkyl group. In particular, those compounds wherein R¹,R², R³ and R⁴ each represents a hydrogen atom or a substituted orunsubstituted alkyl group are preferable (provided that R¹, R², R³ andR⁴ do not all represent a hydrogen atom at the same time). Above all,those wherein R¹, R² and R³ represent a hydrogen atom and R⁴ asubstituted or unsubstituted alkyl group; those wherein R¹ and R³represent a hydrogen atom, and R² and R⁴ a substituted or unsubstitutedalkyl group; or those wherein R¹ and R² represent a hydrogen atom, andR³ and R⁴ a substituted or unsubstituted alkyl group (R³ and R⁴optionally together forming a hetero ring).

When n is 1, X¹ preferably represents --CO--, R⁴ preferably represents asubstituted or unsubstituted amino group, and R¹ to R³ each preferablyrepresents a hydrogen atom or a substituted or unsubstituted alkylgroup.

The alkyl group represented by R¹ to R⁴ more preferably contains 1 to 10carbon atoms, and most preferably 1 to 7 carbon atoms. Preferablesubstituents for the alkyl group include a hydroxy group, a carboxylicacid group, a sulfo group and a phosphonic acid group. When two or moresubstituents exist, they may be the same or different from each other.

The compounds represented by the general formula (II) may form a bisderivative, a tris derivative or a polymer bound through R¹, R², R³ orR⁴.

Examples of the compounds represented by general formula (II) areillustrated below which, however, are not limitative. ##STR12##

As specific examples other than the above-described compounds, there areillustrated those which are described in, for example, JP-A No.63-146041 (Japanese Patent Application No. 61-170756), pp. 11-24, JP-ANo. 63-146042 (Japanese Patent Application No. 6-171682), pp. 12-22, andJP A-63-146043 (Japanese Patent Application No. 61-173468), pp. 9-19.

Many of the compounds represented by general formula (II) arecommercially available, and may be synthesized according to generalsynthesizing processes described in, for example, Organic Synthesis,Coll. vol. 2, pp. 208-213; Jour. Amer. Chem. Soc., 36, 1747 (1914);Abura Kagaku (Oil Chemistry), 24, 31 (1975); Jour. Org. Chem., 25, 44(1960); Yakugaku Zasshi (Journal of Pharmaceutics), 91, 1127 (1971);Organic Synthesis, Coll. vol. 1, p. 450; Shin Jikken Kagaku Koza (NewLecture on Experimental Chemistry), Vol. 14, III, pp. 1621-1628(published by Maruzen); Beil. 2, 559; Beil., 3, 117; E. B. Mohr et al.,Inorg. Syn., 4, 32 (1953); F. J. wilson, E. C. Pickering, J. Chem. Soc.,123, 394 (1923); N. J. Leonard & J. H. Boyer, J. Org. Chem., 15, 42(1950); Organic Synthesis, Coll. vol. 5, p. 1055; P. A. S. Smith,Derivatives of hydrazine and other hydronitrogens having N--N bonds, pp.120-124 and 130-131, THE BENJAMIN/CUMMINGS COMPANY, (1983); Staniey R.Sandier Waif Karo, Organic Functional Group Preparations, Vol. 1, SecondEdition, p. 457.

The compounds of general formula (II) are added in amounts of 0.01 g to50 g, preferably 0.1 g to 30 g, more preferably 0.5 g to 10 g, per literof color developer.

Color developers used in the present invention are described below.

Color developers used in the present invention contain known aromaticprimary amine color developing agents. Preferable examples thereof arep-phenylenediamine derivatives, and typical examples thereof areillustrated below which, however, are not limitative.

D-1: N,N-Diethyl-p-phenylenediamine

D-2: 4-(N-Ethyl-N-(β-hydroxyethyl)amino)aniline

D-3: 2-Methyl-4-(N-ethyl-N-(β-hydroxyethyl)amino) aniline

4-Amino-3-methyl-N-ethyl-N-(β-(methanesulfonamido)-ethyl)aniline

These p-phenylenediamine derivatives may be in a salt form such assulfates, hydrochlorides, sulfites or p-toluenesulfonates. The aromaticprimary amine developing agents are used in amounts of, preferably about0.1 g to about 20 g, more preferably about 0.5 g to about 10 g, perliter of color developing solution.

Particularly, the use of color-developing agent D-4 in the presence ofthe compounds of general formula (I) depresses an increase of fog and,therefore, serves to provide good photographic properties, thus beingpreferable.

Sulfite ion known as preservative is not substantially incorporated inthe color developer of the present invention. The term "notsubstantially" permits one to add in an amount not influencingphotographic properties, specifically in an amount of 0 to 0.005mol/liter, preferably 0 to 0.002 mol/liter.

As compounds which directly preserve the color-developing agents,various hydroxylamines, hydroxamic acids described in JP-A No. 63-43138,phenols described in JP-A No. 63-44657 and JP-A No. 63-58443,α-hydroxyketones and α-aminoketones described in JP-A No. 63-44656and/or various sugars described in JP-A No. 63-36244 are preferablyadded. If necessary, these compounds may be used in combination withmonoamines described in JP-A No. 63-4235, JP-A No. 63-24254, JP-A No.63-21647, JP-A No. 63-146040, JP-A No. 63-27841 and JP-A No. 63-25654,diamines described in JP-A No. 63-43139 and JP-A No. 63-30845,polyamines described in JP-A No. 63-26655, polyamines described in JP-ANo. 63-44655, nitroxy radicals described in JP-A No. 63-53551, alcoholsdescribed in JP-A No. 63-43140 and JP-A No. 63-53549, oximes describedin JP-A No. 63-56654, and tertiary amines described in EP-A-266797.

In addition, various metals described in JP-A No. 57-44148 and JP-A No.57-53749, salicylic acids described in JP-A No. 59-180588, alkanolaminesdescribed in JP-A No. 54-3532, polyethyleneimines described in JP-A No.56-94349, and aromatic polyhydroxy compounds described in U.S. Pat. No.3,746,544 are preferably used. Particularly, addition of aromaticpolyhydroxy compounds, triethanolamine, and compounds described inEP-A-266797 is preferable.

The color developer of the present invention preferably does notsubstantially contain benzyl alcohol in view of preventing an increasein fog and stain after processing. That is, "not substantiallycontaining" means to contain benzyl alcohol in an amount of up to 5.0ml, preferably up to 2 ml, per liter of the color developer, morepreferably 0 ml.

The color developer used in the present invention preferably has a pH of9 to 12, more preferably 9 to 11, and may further contain knowndeveloper components.

In order to keep pH in the above-described range, various buffer agentsare preferably used. As the buffer agents, carbonic acid salts,phosphoric acid salts, boric acid salts, tetraboric acid salts,hydroxybenzoic acid salts, glycine salts, N,N-dimethylglycine salts,leucine salts, norleucine salts, guanine salts,3,4-dihydroxyphenylalanine salts, alanine salts, aminobutyric acidsalts, 2-amino-2-methyl-1,3-propanediol salts, valine salts, prolinesalts, trishydroxyaminomethane salts, lysine salts, etc. may be used. Inparticular, carbonic acid salts, phosphoric acid salts, tetraboric acidsalts and hydroxybenzoic acid salts are excellent in solubility andbuffering ability in the higher pH region of more than 9.0, do not exertdetrimental influences (for example, fogging) on photographic propertieswhen added to color developers, and are inexpensive. Thus, their use isparticularly preferable.

Specific examples of these buffer agents include sodium carbonate,potassium carbonate, sodium bicarbonate, potassium bicarbonate,trisodium phosphate, tripotassium phosphate, disodium phosphate,dipotassium phosphate, sodium borate, potassium borate, sodiumtetraborate (borax), potassium tetraborate, sodium o-hydroxybenzoate(sodium salicylate), potassium o-hydroxybenzoate, sodium5-sulfo-2-hydroxybenzoate (sodium 5-sulfosalicylate), potassium5-sulfo-2-hydroxybenzoate (potassium 5-sulfosalicylate), etc. However,these do not limit the present invention in any way.

These buffer agents are added to color developers in amounts ofpreferably not less than 0.1 mol/liter, particularly preferably 0.1mol/liter to 0.4 mol/liter.

In addition, various chelating agents may be used in the color developeras agents for preventing precipitation of calcium or magnesium or forimproving the stability of the color developer.

As the chelating agents, organic acid compounds are preferable, whichare exemplified by the aminopolycarboxylic acids described in JP-B No.48-30496 and JP-B No. 44-30232, organophosphonic acids described in JP-ANo. 56-97347, JP-B No. 56-39359 and West German Pat. No. 2,227,639,phosphonocarboxylic acids described in JP-A No. 52-102726, JP-A No.53-42730, JP-A No. 54-121127, JP-A No. 55-126241 and JP-A No. 55-659506,and compounds described in JP-A No. 58-195845, JP-A No. 58-203440 andJP-B No. 53-40900. Specific examples thereof are illustrated belowwhich, however, are not limitative.

Nitrilotriacetic acid, diethylenetriaminepentaacetic acid,ethylenediaminetetraacetic acid, N,N,N-trimethylenephophosphonic acid,ethylenediamine-N,N,N',N'-tetramethylene phosphonic acid,trans-cyclohexanediaminetetraacetic acid, 1,2-diaminopropanetetraaceticacid, glycol ether diaminetetraacetic acid,ethylenediamine-o-hydroxyphenylacetic acid,2-phosphonobutane-1,2,4-tricarboxylic acid,1-hydroxyethylidene-1,1-diphosphonic acid,N,N'-bis(2-hydroxybenzyl)ethylenediamine-N,N'-diacetic acid, etc.

Two or more of these chelating agents may be used in combination as thecase demands.

These chelating agents are added in a sufficient amount to mask metalions in the color developer, for example, about 0.1 g to about 10 g perliter.

An arbitrary development accelerator may be added to the color developeras the case demands. However, in view of prevention of environmentalpollution, convenience of preparation, and prevention of fogging, thecolor developer of the present invention preferably does notsubstantially contain benzyl alcohol.

The compounds to be used in the present invention represented by theforegoing general formula (II) provide remarkable effects as tostability of color developers not substantially containing benzylalcohol.

As other development accelerators, thioether compounds described in JP-BNo. 37-16088, JP-B No. 37-5987, JP-B No. 38-7826, JP-B No. 44-12380,JP-B No. 45-9019 and U.S. Pat. No. 3,813,247, p-phenylenediaminecompounds described in JP-A No. 52-49829 and JP-A No. 50-15554,quaternary ammonium salts described in JP-A No. 50-137726, JP-B No.44-30074, JP-A No. 56-156826 and JP-A No. 52-43429, amine compoundsdescribed in U.S. Pat. Nos. 2,494,903, 3,128,182, 4,230,796 and3,253,919, JP-B No. 41-11431, U.S. Pat. Nos. 2,482,546, 2,596,926 and3,582,346, polyalkylene oxides described in JP-B No. 37-16088, JP-B No.42-25201, U.S. Pat. No. 3,128,183, JP-B No. 41-11431, JP-B42-23883 andU.S. Pat. No. 3,532,501, and 1-phenyl-3-pyrazolidones and imidazoles maybe added as the case demands.

In the present invention, any antifogging agent(s) may be added as thecase demands. As the antifogging agents, alkali metal halides such assodium chloride, potassium bromide and potassium iodide and organicantifogging agents may be used. As typical examples of organicantifogging agents, there are illustrated nitrogen-containingheterocyclic compounds such as benzotriazole, 6-nitrobenzimidazole,5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole,5-chlorobenzotriazole, 2-thiazolyl-benzimidazole,2-thiazolylmethyl-benzimidazole, indazole, hydroxyazaindolidine andadenine.

The color developer used in the present invention preferably contains afluorescent brightening agent. As the fluorescent brightening agent,4,4'-diamino-2,2-disulfostilbene compounds are preferable. They areadded in amounts of 0 g to 5 g/liter, preferably 0.1 g to 4 g /liter.

Various surface active agents such as alkylsulfonic acids, arylsulfonicacids, aliphatic carboxylic acids, aromatic carboxylic acids, etc., maybe added as the case demands.

The processing temperature of the color developer of the presentinvention is generally 20° to 50 ° C. and more preferably 30° to 40 ° C.The processing time is generally 20 seconds to 5 minutes, and morepreferably 30 seconds to 2 minutes. The replenishing amount is desirablyminimized, and is generally 20 to 600 ml, preferably 50 to 300 ml, morepreferably 100 to 200 ml, per m² of light-sensitive material.

The color photographic material used in the present invention isgenerally subjected to bleaching or bleach-fixing after developing.

A bleaching solution, a bleach-fixing solution, and a fixing solutionused in the present invention are described below.

As bleaching agents used in the bleaching solution or bleach-fixingsolution in the method of the present invention, any conventionalbleaching agents may be used, with iron(III) organic complex salts (forexample, complex salts of aminopolycarboxylic acids such asethylenediaminetetraacetic acid or diethylenetriaminepentaacetic acid,aminopolyphosphonic acid, phosphonocarboxylic acid and organophosphonicacid) or iron(III) salts of organic acids (for example, citric acid,tartaric acid and malic acid); persulfates; and hydrogen peroxide beingpreferable.

Of these, iron(III) organic complex salts are particularly preferable inview of rapid processing and prevention of environmental pollution.Aminopolycarboxylic acids, aminopolyphosphonic acids or organophosphonicacids, or their salts useful for forming the iron(III) organic complexsalts are illustrated below: ethylenediaminetetraacetic acid,diethylenetriaminepentaacetic acid, 1,3-diaminopropanetetraacetic acid,propylenediaminetetraacetic acid, nitrilotriacetic acid,cyclohexanediaminetetraacetic acid, methyliminodiacetic acid,iminodiacetic acid, glycol ether diaminetetraacetic acid, etc.

These compounds may be in the form of sodium salts, potassium salts,lithium salts and ammonium salts. Of these, iron(III) complex salts ofethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid,cyclohexanediaminetetraacetic acid, 1,3-diaminopropanetetraacetic acid,and methyliminodiacetic acid are preferred due to their high bleachingability.

These ferric ion complex salts may be used in complex salt form, or maybe formed in solution by using a ferric salt such as ferric sulfate,ferric chloride, ferric nitrate, ferric ammonium sulfate or ferricphosphate and a chelating agent such as an aminopolycarboxylic acid,aminopolyphosphonic acid or phosphonocarboxylic acid. The chelatingagent may be added in an amount more than that amount necessary forforming the ferric ion complex salt. Of the iron complexes,aminopolycarboxylic acid/iron complexes are preferable, which are addedin amounts of 0.01 to 1.0 mol/liter, preferably 0.05 to 0.50 mol/liter.

Various compounds may be used as bleaching accelerator in the bleachingsolution, bleach-fixing solution and/or pre-baths thereof. For example,mercapto group- or disulfido bond-containing compounds described in U.S.Pat. No. 3,893,858, West German Pat. No. 1,290,812, JP-A No. 53-95630and Research Disclosure, 17129 (July 1978), thiourea compounds describedin JP-B No. 45-8506, JP-A No. 52-20832, JP-A No. 53-32735 and U.S. Pat.No. 3,706,561, and halides such as iodine ion and bromine ion arepreferable due to their excellent bleaching ability.

Further, the bleaching or bleach-fixing solution used in the presentinvention may contain bromide (for example, potassium bromide, sodiumbromide or ammonium bromide), chloride (for example, potassium chloride,sodium chloride or ammonium chloride) or iodide (for example, ammoniumiodide) as a rehalogenating agent. If necessary, one or more inorganicacids, organic acids and alkali metal salts or ammonium salts thereofhaving a buffering ability, such as boric acid, borax, sodiummetaborate, acetic acid, sodium acetate, sodium carbonate, potassiumcarbonate, phosphorous acid, phosphoric acid, sodium phosphate, citricacid, sodium citrate and tartaric acid, or anti-corrosives such asammonium nitrate and guanidine may be added thereto.

Fixing agents used in the bleach-fixing or fixing solution used in themethod of the present invention are known conventional fixing agents,i.e., water-soluble silver halide dissolving agents such as thiosulfates(e.g., sodium thiosulfate and ammonium thiosulfate), thiocyanates (e.g.,sodium thiocyanate and ammonium thiocyanate) , thioether compounds(e.g., ethylenebisthioglycolic acid and 3,6-dithia-1,8-octanediol) andthioureas. These may be used alone or as a combination of two or more.Special bleach-fixing solutions comprising a combination of a fixingagent and a large amount of halide such as potassium iodide described inJP-A No. 55-155354 may also be used. In the present invention, the useof thiosulfates, particularly ammonium thiosulfate, is preferred. Theamount of fixing agent ranges from 0.3 to 2 mols, preferably 0.5 to 1.0mol, per liter.

The bleach-fixing solution or fixing solution used in the presentinvention preferably has a pH of 3 to 10, more preferably 5 to 9.

The bleach-fixing solution may further contain various fluorescentbrightening agents, defoaming agents, surfactants, polyvinyl pyrrolidoneand organic solvents (e.g., methanol).

The bleach-fixing or fixing solution of the present invention cancontain, as a preservative, sulfite ion-releasing compounds such assulfites (e.g., sodium sulfite, potassium sulfite and ammonium sulfite),bisulfites (e.g., ammonium bisulfite, sodium bisulfite and potassiumbisulfite), and metabisulfites (e.g., potassium metabisulfite, sodiummetabisulfite, and ammonium metabisulfite). These compounds areincorporated in amounts of preferably about 0.02 to about 0.50mol/liter, more preferably 0.04 to 0.40 mol/liter, calculated as sulfiteion.

As the preservatives, sulfite salts are commonly added. However,ascorbic acid, carbonyl-bisulfite adducts, carbonyl compounds, etc., mayalso be added.

Further, buffering agents, fluorescent brightening agents, chelatingagents, defoaming agents, antifungal agents, etc., may be added as thecase demands.

After being subjected to the desilvering processing of fixing orbleach-fixing, the silver halide color photographic material used in thepresent invention is generally subjected to water-washing and/orstabilizing.

The amount of washing water used in the water-washing washing step canbe selected from a wide range depending upon the characteristics oflight-sensitive materials (for example, the kinds of used materials suchas couplers), uses, and, further, conditions such as the temperature ofthe washing water, number of washing tanks (or steps), replenishingmanner (such as counter current or direct current), and the like. Ofthese, the relationship between the number of water-washing tanks andthe amount of water in a multi-stage counter current process can bedetermined according to Journal of the Society of Motion Picture andTelevision Engineers, Vol. 64, pp. 248-253 (May 1955). The number ofsteps in multi-stage counter current process is usually 2 to 6,preferably 2 to 4.

The multi-stage counter current process enables one to greatly reducethe amount of washing water. For example, the amount of washing watermay be 0.5 liter to 1 liter per m² of light-sensitive materials.However, such involves various problems such as the propagation ofbacteria caused by a prolonged residence time of the washing water in atank leads to the production of suspended matter which adheres tolight-sensitive materials. In processing the color light-sensitivematerial of the present invention, reducing the concentration of calciumand magnesium ions described in JP-A No. 62-288838 intended to solve theproblem is extremely effective. In addition, isothiazolone compounds andthiabendazole described in JP-A No. 57-8542, chlorine-containingcontaining bactericides such as sodium chloroisocyanurate, etc., andbactericides such as benzotriazoles and copper ion described in HiroshiHoriguchi; Bokin-bobai No Kagaku (Antibacterial and AntifungalChemistry), Eisei Gijutsu-kai; Biseibutsu No Mekkin, Sakkin, BobaiGijutsu (Sterilizing and antifungal techniques against microorganisms),and Nihon Bokin-bobai Gakkai; Bokin-bobaizai Jiten (Antibacterial andantifungal book) can be used.

Further, the washing water may contain a surfactant as a draining agentand may contain a chelating agent represented byethylenediaminetetraacetic acid as a hard-water softener.

The pH of the washing water used in processing the light-sensitivematerial of the present invention generally ranges from 4 to 9,preferably 5 to 8. The temperature and time of washing may be varieddepending upon the characteristics of the light-sensitive material, enduse, etc., but, in general, a washing temperature of 15° to 45° C. and awashing time of 20 seconds to 10 minutes, preferably a washingtemperature of 25° to 40° C. and a washing time of 30 seconds to 5minutes, are employed.

The light-sensitive material may be processed with a stabilizingsolution subsequent to the above-described water-washing step ordirectly without the water-washing step. To the stabilizing bath areadded compounds having image-stabilizing ability. For example, there areillustrated aldehyde compounds represented by formalin, buffering agentsfor adjusting the film pH to a level suited for stabilizing dyes, andammonium compounds. In addition, in order to prevent the propagation ofbacteria in the solution or to impart antifungal properties to processedlight-sensitive materials, various bactericides and fungicideshereinbefore described may be used.

Further, a surfactant, a fluorescent brightening agent, and a hardenermay be added thereto. In the case of directly conducting the stabilizingprocedure in the processing of the present invention without thewater-washing step, known techniques described in JP-A No. 57-8543, JP-ANo. 58-14834, JP-A No. 59-184343, JP-A No. 60-220345, JP-A No. 238832,JP-A No. 60-239784, JP-A No. 60-239749, JP-A No. 61-4054, JP-A No.61-118749, etc., may be employed.

In addition, the use of chelating agents such as1-hydroxyethylidene-1,1-diphosphonic acid andethylenediamine-tetramethylenephosphonic acid, and magnesium or bismuthcompounds is also a preferable embodiment for the stabilizing solution.

The solution used int he washing and/or stabilizing step may be used inthe prior step. As one example thereof, an over-flow of washing waterwhose amount is decreased by the multi-stage counter current manner isintroduced into its pre-bath of bleach-fixing bath, into which aconcentrated solution is replenished, thus the amount of waste solutionbeing reduced.

The method of the present invention may be applied in any processingthat uses a color developer. For example, it may be applied to theprocessing of color papers, color reversal papers, color direct positivelight-sensitive materials, color positive films, color negative films,color reversal films, etc., particularly preferably color papers andcolor reversal papers.

As the silver halide emulsion for the light-sensitive material to beused in the present invention, those emulsions which have any halidecomposition, such as silver iodobromide, silver bromide, silverchlorobromide and silver chloride, may be used. For example, in the caseof conducting accelerated processing or low-replenishing processing ofcolor papers or the like, silver chlorobromide emulsions containing 60mol % or more silver chloride or silver chloride emulsions arepreferable, with the content of silver chloride being particularlypreferably 80 to 100 mol %. In the case where high speed is required andwhere fogging upon preparation, during storage and/or upon processing oflight-sensitive material is required by to be depressed to aparticularly low level, silver chlorobromide emulsions containing 50 mol% or more silver bromide or silver bromide emulsions (optionallycontaining up to 3 mol % silver iodide) are preferable, with the contentof silver bromide being particularly preferably 70 mol % or more. Forcolor light-sensitive materials for picture taking, silver iodobromideand silver chloroiodobromide are preferable, with the silver iodidecontent preferably being 3 to 15 mol %.

The silver halide grains used in the present invention may have an innerportion and a surface layer different from each other in phasecomposition, may be of a multi-phase structure having a conjunctionstructure, or may wholly comprise a uniform phase. Further, mixturesthereof can be used.

Average grain size (presented in terms of diameter of grains withrespect to spherical or approximately spherical grains or, with cubicgrains, calculated based on projected area taking the edge length asgrain size) of silver halide grains used in the present invention ispreferably 0.1 μm to 2 μm, particularly preferably 0.15 μm to 1.5 μm.Grains size distribution may be narrow or broad, but monodispersedemulsions which have a coefficient of variation (standard deviationvalue/average grain size in the grain size distribution curve of silverhalide emulsion) of within ±20%, particularly preferably with ±15%, arepreferably used in the present invention. In order to obtain asatisfactory gradiation intended for the light-sensitive material, twoor more kinds of monodispersed silver halide emulsions (havingpreferably monodisperse properties falling within the above-describedrange of coefficient of variation) may be used as a mixture in one andthe same layer or separately coated as superposed layers to provideemulsion layers having substantially the same color sensitivity.Further, two or more polydispersed silver halide emulsions or acombination of a monodispersed emulsion and a polydispersed emulsion maybe used as a mixture or by coating as separate and superposed layers.

Silver halide grains used in the present invention may be in a regularcrystal form such as cubic, octahedral, rhombic dodecahedral ortetradecahedral form or a mixture thereof, in an irregular crystal formsuch as spherical, or in a composite form thereof. In addition, tabulargrains are also usable. Emulsions wherein tabular grains having alength-to-thickness ratio of 5 to 8, or 8 or more, account for 50% ormore of the total projected area of the grains may also be used.Emulsions comprising a mixture of these various crystal forms may beused as well. Either surface latent image-forming type silver halidegrains forming a latent image mainly on the surface thereof or internallatent image-forming type grains forming a latent image in the interiorthereof may be used.

The photographic emulsions used in the present invention can be preparedaccording to processes described in Research Disclosure (RD), vol. 170,Item No. 17643 (I, II, III) (December, 1978).

The silver halide emulsions to be used in the present invention areusually subjected to physical ripening, chemical ripening, and spectralsensitization before use. Additives used in these steps are described inResearch Disclosure, vol. 176, No. 17643 (December, 1978) and ResearchDisclosure, vol. 187, No. 18716 (November, 1979). Places where suchadditives are described are tabulated in the table to be shownhereinafter.

Known photographic additives which can be used in the present inventionare also described in the above two Research Disclosure articles, andplaces where they are described are also tabulated in the followingtable.

    ______________________________________                                        Kind of Additive  RD 17643   RD 18716                                         ______________________________________                                         1. Chemical sensitizers                                                                        p. 23      p. 648,                                                                       right col.                                        2. Sensitivity-increasing agents                                                                          "                                                 3. Spectrally sensitizing agents                                                               pp. 23-24  p. 648,                                                                       right col.                                                                    to 649,                                                                       right col.                                        4. Supersensitizing agents                                                                     "          "                                                 5. Brightening agents                                                                          p. 24                                                        6. Antifoggants and stabilizers                                                                pp. 24-25  p. 649,                                                                       right col.                                        7. Couplers      p. 25                                                        8. Organic solvents                                                                            p. 25                                                        9. Light absorbents and                                                                        pp. 25-26  p. 649,                                            filter dyes                right col.                                                                    to 650,                                                                       left col.                                        10. UV ray absorbents                                                                           "          "                                                11. Stain-preventing agents                                                                     p. 25,     p. 650 left -                                                      right col. right col.                                       12. Dye image stabilizers                                                                       p. 25                                                       13. Hardeners     p. 26      p. 651,                                                                       left col.                                        14. Binders       p. 26      "                                                15. Plasticizers and lubricants                                                                 p. 27      p. 650,                                                                       right col.                                       16. Coating aids and surfactants                                                                pp. 26-27  "                                                17. Antistatic agents                                                                           p. 27      "                                                ______________________________________                                    

Various couplers may be used in the present invention other than themagenta couplers of general formula (I). The term "color couplers" asused herein means those compounds which undergo a coupling reaction withan oxidation product of aromatic primary amine developing agent toproduce dyes. Typical examples of useful color couplers includenaphtholic or phenolic couplers, pyrazolone or pyrazoloazole typecompounds, and open-chain or heterocyclic ketomethylene compounds.Specific examples of such cyan, magenta, and yellow couplers used in thepresent invention are described in those patents which are cited inResearch Disclosure, (RD), 17643 (December, 1978), Item VII-D and ibid.,18717 (November, 1979).

Color couplers incorporated in the light-sensitive materials preferablyhave a ballast group or are polymerized to acquire diffusion resistance.In comparison with 4-equivalent color couplers having hydrogen atoms incoupling active sites, two equivalent color couplers substituted bycoupling-off groups in coupling active sites permit one to reduce theamount of coated silver. Couplers which can form color dyes withsuitable diffusibility, non-color forming couplers, DIR couplers capableof releasing a development inhibitor upon coupling reaction, or couplerscapable of releasing a development accelerator may also be used.

Typical examples of yellow couplers which can be used in the presentinvention include oil protected type acylacetamide couplers. Specificexamples thereof are described in U.S. Pat. Nos. 2,407,210, 2,875,057and 3,265,506, etc. In the present invention, the use of two equivalentyellow couplers is preferable, and typical examples thereof includeyellow couplers of the oxygen atom coupling-off type described in U.S.Pat. Nos. 3,408,194, 3,447,928, 3,933,501 and 4,022,620, etc., andyellow couplers of the nitrogen atom coupling-off type described in JP-BNo. 55-10739, U.S. Pat. Nos. 4,401,752 and 4,326,024, ResearchDisclosure, RD 18053 (April, 1979), British Pat. No. 1,425,020, WestGerman Patent Application (OPI) Nos. 2,219,917, 2,261,361, 2,329,587 and2,433,812, etc. α-Pivaloylacetanilide type couplers are excellent infastness, particularly light fastness, of colored dyes, whereasα-benzoylacetanilide type couplers provide high coloration density.

Magenta couplers which can be used in the present invention include oilprotected type indazolone or cyanoacetyl, preferably pyrazoloazole type(e.g., pyrazolone) couplers. Of the 5-pyrazolone couplers, those whichare substituted by an arylamino group or an acylamino group in the3-position are preferable in view of the hue and coloration density ofthe colored dyes. Typical examples thereof are described in U.S. Pat.Nos. 2,311,082, 2,343,703, 2,600,788, 2,908,573, 3,062,653, 3,152,896and 3,936,015. As coupling-off groups for 2-equivalent 5-pyrazolonecouplers, nitrogen atoms coupling-off groups described in U.S. Pat. No.4,310,619 and arylthio groups described in U.S. Pat. No. 4,351,897 areparticularly preferable. The ballast group-containing 5-pyrazolonecouplers described in European Pat. No. 73,636 provide high colorationdensity.

Cyan couplers which can be used in the present invention include oilprotected type naphtholic and phenolic couplers. Typical examplesthereof include naphtholic couplers described in U.S. Pat. No.2,474,293, preferably oxygen atom coupling-off type 2-equivalentnaphtholic couplers described in U.S. Pat. Nos. 4,052,212, 4,146,396,4,228,233 and 4,296,200. Specific examples of the phenolic couplers aredescribed in U.S. Pat. Nos. 2,369,929, 2,801,171, 2,772,162, 2,895,826,etc. Cyan couplers capable of forming dyes fast against high humidityand high temperature are preferably used in the present invention, andtypical examples thereof include phenolic cyan couplers having an alkylgroup containing 2 or more carbon atoms at the m-position of the phenolnucleus described in U.S. Pat. No. 3,772,002,2,5-diacylamino-substituted phenolic couplers described in U.S. Pat.Nos. 2,772,162, 3,758,308, 4,126,396, 4,334,011, and 4,327,173, WestGerman Patent Application (OLS) No. 3,329,729, and JP-A No. 59-166956,etc., and phenolic couplers having a phenylureido group in the2-position and an acylamino group in the 5-position, described in U.S.Pat. Nos. 3,446,622, 4,333,999, 4,451,559 and 4,427,767, etc.

Graininess can be improved by using those couplers which form dyes withproper diffusibility. As such couplers forming diffusible dyes, U.S.Pat. No. 4,366,237 and British Pat. No. 2,125,570 describe specificexamples of magenta couplers, and European Pat. No. 96,570 and WestGerman Patent Application (OLS) No. 3,234,533 describe specific examplesof yellow, magenta, or cyan couplers.

The dye-forming couplers and the above-described special couplers mayform a dimer or higher polymer. Typical examples of polymerizeddye-forming couplers are described in U.S. Pat. Nos. 3,451,820 and4,080,211. Specific examples of polymerized magenta couplers aredescribed in British Pat. No. 2,102,173 and U.S. Pat. No. 4,367,282.

Two or more of the various couplers used in the present invention may beused in one and the same light-sensitive layer, or one and the samecompound may be used in two or more layers for obtaining photographiccharacteristics required for light-sensitive materials.

The couplers used in the present invention may be introduced intolight-sensitive materials according to various known dispersingprocesses. Examples of high-boiling organic solvents to be used in theoil-in-water dispersing process are described in, for example, U.S. Pat.No. 2,322,027. Steps and effects of latex dispersing processes, andspecific examples of latexes for impregnation are described in U.S. Pat.No. 4,199,363, West German Patent Application (OLS) Nos. 2,541,274 and2,541,230.

Standard amounts of color couplers other than the magenta couplers ofgeneral formula (I) are 0.001 to 1 mol per mol of light-sensitive silverhalide and, preferably, 0.01 to 0.5 mol with respect to yellow couplers,0.003 to 0.3 mol with respect to magenta couplers, and 0.002 to 0.3 molwith respect to cyan couplers.

The photographic light-sensitive material used in the present inventionis coated on a conventional flexible support such as a plastic film (forexample, cellulose nitrate, cellulose acetate, or polyethyleneterephthalate) or paper or on a rigid support such as glass. Supportsand coating processes are described in detail in Research Disclosure,vol. 176, Item 17643, XV (p. 27) and XVII (p. 28) (December 1978).

In the present invention, a reflective support is preferably used."Reflective supports" serve to raise reflectivity to make distinct thedye image formed in the silver halide emulsion layers. Such reflectivesupports include those which are prepared by coating a hydrophobic resincontaining dispersed therein a light-reflecting substance such astitanium oxide, zinc oxide, calcium carbonate or calcium sulfate on asupport and those which comprise a hydrophobic resin containingdispersed therein the light-reflecting substance.

The present invention is now described in greater detail by reference tothe following examples which, however, are not to be construed aslimiting the present invention in any way.

EXAMPLE 1

Multi-layer color photographic print papers having the stratum structureshown in Table A on a paper support double-laminated with polyethylenewere prepared with changing the magenta couplers used. Coating solutionswere prepared as follows.

Preparation of a coating solution for forming the first layer

27.2 ml of ethyl acetate and 7.7 ml of solvent (c) were added to 19.1 gof yellow coupler (a) and 4.4g of color image stabilizer (b), and theresulting solution was emulsified and dispersed in 185 ml of a 10%gelatin aqueous solution containing 8 ml of 10% sodiumdodecylbenzenesulfonate. On the other hand, a silver chlorobromideemulsion(containing 90.0 mol % of silver bromide and 70 g/kg of Ag)containing 5.0×10⁻⁴ mol of the following blue-sensitive sensitizing dyeper mol silver was prepared. The aforesaid emulsion dispersion and thisemulsion were mixed with each other according to the formulation inTable A to prepare a coating solution for forming the first layer.Coating solutions for forming the second to seventh layers were alsoprepared in the same manner as with the coating solution for forming thefirst layer. As gelatin hardener for each layer, sodium salt of1-hydroxy-2,5-dichloro-s-triazine was used.

Spectrally sensitizing dyes for respective layers are shown below.##STR13##

To the red-sensitive emulsion layer was added the following compound inan amount of 2.6×10⁻³ mol per of silver halide. ##STR14##

1-(5-methylureidophenyl)-5-mercaptotetrazole was added to theblue-sensitive emulsion layer, green-sensitive emulsion layer andred-sensitive emulsion layer in amounts of 8.5×10⁻⁵ mol, 7.7×10⁻⁴ mol,and 2.5×10⁻⁴ mol, respectively, per mol of silver halide.

4-hydroxy-6-methyl-1,2,3a,7-tetrazaindene was added to theblue-sensitive emulsion layer and the green-sensitive emulsion layer inamounts of 1.2×10⁻² mol and 1.1×10⁻² mol, respectively, per mol ofsilver halide.

The following dyes were added to an intermediate layer for preventingirradiation: ##STR15##

                                      TABLE A                                     __________________________________________________________________________    Layer Main Formulation  Used Amount                                           __________________________________________________________________________    7th layer                                                                           Gelatin           1.33  g/m.sup.2                                       (protec-                                                                            Acryl-modified copolymer of                                                                     0.17  "                                               tive layer)                                                                         polyvinvyl alcohol (modification                                              degree: 17%)                                                                  Liquid paraffin   0.03  "                                               6th layer                                                                           Gelatin           0.53  g/m.sup.2                                       (UV ray-                                                                            UV ray absorbent (i)                                                                            0.21  "                                               absorbing                                                                           Solvent (k)       0.08  "                                               layer)                                                                        5th layer                                                                           AgClBr emulsion (AgBr:70 mol %)                                                                 0.23  g/m.sup.2 of Ag                                 (red- Gelatin           1.34  g/m.sup.2                                       sensitive                                                                           Cyan coupler (l)  0.34  "                                               layer)                                                                              Color image stabilizer (m)                                                                      0.17  "                                                     Polymer (n)       0.40  "                                                     Solvent (o)       0.23  "                                               4th layer                                                                           Gelatin           1.58  g/m.sup.2                                       (UV ray-                                                                            UV ray absorbent (i)                                                                            0.62  "                                               absorbing                                                                           Color mixing-preventing                                                                         0.05  "                                               layer)                                                                              agent (j)                                                                     Solvent (k)       0.24  "                                               3rd layer                                                                           AgClBr emulsion (AgBr:80 mol %)                                                                 0.16  g/m.sup.2 of Ag                                 (green-                                                                             Gelatin           1.79  g/m.sup.2                                       sensitive                                                                           Magenta coupler (e)                                                                             3.5 × 10.sup.-4                                                               mol/m.sup.2                                     layer)                                                                              Color image stabilizer (f)                                                                      0.20  g/m.sup.2                                             Color image stabilizer (g)                                                                      0.01  "                                                     Solvent (h)       0.65  "                                               2nd layer                                                                           Gelatin           0.99  g/m.sup.2                                       (color-                                                                             Color mixing-preventing                                                                         0.08  "                                               mixing                                                                              agent (d)                                                               preventing                                                                    layer)                                                                        1st layer                                                                           AgClBr emulsion (AgBr:90 mol %)                                                                 0.26  g/m.sup.2 of Ag                                 (blue-                                                                              Gelatin           1.83  g/m.sup.2                                       sensitive                                                                           Yellow coupler (a)                                                                              0.83  "                                               layer)                                                                              Color image stabilizer (b)                                                                      0.19  "                                                     Solvent (c)       0.35  "                                               Support                                                                             Polyethylene-laminated paper (containing a                                    white pigment (TiO.sub.2) and a bluish dye                                    (Ultramarine) in polyethylene on the first                                    layer-coated side)                                                      __________________________________________________________________________

Structural formulae of the compounds such as couplers used in Example 1are as follows. ##STR16##

Color photographic printing papers containing varying magenta couplersas shown in Table 1 were prepared. The resulting photographic paperswere exposed through an optical wedge, then processed according to thefollowing steps.

    ______________________________________                                        Processing Step                                                                             Temp.        Time                                               ______________________________________                                        Color development                                                                           38° C.                                                                              1 min. and 40 sec.                                 Bleach-fixing 30-34° C.                                                                           1 min. and 00 sec.                                 Rinsing (1)   30-34° C.                                                                           20 sec.                                            Rinsing (2)   30-34° C.                                                                           20 sec.                                            Rinsing (3)   30-34° C.                                                                           20 sec.                                            Drying        70-80° C.                                                                           50 sec.                                            ______________________________________                                         (Three-tank counter current manner of rinsing (3) to (1) was employed.)  

The formulations of respective processing solutions are as follows.

    ______________________________________                                        Color developer                                                               ______________________________________                                        Water                     800 ml                                              Compound A                See Table 1.                                        Triethanolamine           8.0 g                                               Diethylenetriaminepentaacetic acid                                                                      1.0 g                                               1-Hydroxyethylidene-1,1-diphosphonic                                                                    2.0 g                                               acid (60%)                                                                    Nitrilotriacetic acid     2.0 g                                               Benzyl alcohol            See Table 1.                                        Diethylene glycol         10 ml                                               Sodium sulfite            See Table 1.                                        Potassium bromide         0.5 g                                               Potassium carbonate       30 g                                                4-Amino-3-methyl-N-ethyl-N-(β-(methane-                                                            5.5 g                                               sulfonamido)ethyl)aniline sulfate                                             Fluorescent brightening agent (WHITEX                                                                   1.5 g                                               4B, made by Sumitomo Chemical Co., Ltd.)                                      Water to make             1,000 ml                                            pH                        10.25                                               ______________________________________                                        Bleach-fixinq solution                                                        ______________________________________                                        Water                     400 ml                                              Ammonium thiosulfate (70%)                                                                              200 ml                                              Sodium sulfite            20 g                                                Iron (III) ammonium ethylenediamine-                                                                    60 g                                                tetraacetate                                                                  Disodium ethylenediamine- 10 g                                                tetraacetate                                                                  Water to make             1,000 ml                                            pH (25° C.)        7.00                                                ______________________________________                                        Rinsing solution                                                              ______________________________________                                        Benzotriazole             1.0 g                                               Ethylenediamine-N,N,N'N'-tetramethyl-                                                                   0.3 g                                               enephosphonic acid                                                            Water to make             1,000 ml                                            pH (25° C.)        7.50                                                ______________________________________                                    

On the other hand, part of each of the above-described color developerswas taken in a 1-liter beaker, and was allowed to stand at 40° C. for 30days in an open state. The thus aged solutions were also used in theabove-described processing.

Processing using the color developers which were allowed to stand for 30days (aged solutions) were referred to as aged solution tests, andprocessings using color developers before having been allowed to stand(fresh solutions) were referred to as fresh solution tests.

The photographic properties obtained by the fresh solution tests and theaged solution tests are tabulated in Table 1.

Photographic properties are presented in terms of D_(min) and gradationof magenta density.

D_(min) represents a minimum density, and gradation is presented interms of the change in density from the point of 0.5 in density to thepoint on 0.3 in log E higher exposure side.

                                      TABLE 1                                     __________________________________________________________________________            Additives                                                                     Compound A                                                                           Benzyl                                                                            Sodium                                                                              Photographic properties                              Magenta (0.05  alcohol                                                                           sulfite                                                                             Fresh soln.                                                                            Aged soln.Dmin                              No.                                                                              coupler                                                                            mol/l  ml/l                                                                              mol/l D.sub.min                                                                        Gradation                                                                           Dmin                                                                              Gradation                                                                           Remarks                           __________________________________________________________________________     1 M-(a)*.sup.1                                                                       II-(a)*.sup.3                                                                        15  1.5 × 10.sup.-2                                                               0.13                                                                             0.72  0.30                                                                              0.85  Comparative                                                                   Example                            2 "    "      --  1.5 × 10.sup.-2                                                               0.13                                                                             0.69  0.23                                                                              0.83  Comparative                                                                   Example                            3 "    "      --  --    0.12                                                                             0.71  0.24                                                                              0.81  Comparative                                                                   Example                            4 "    II-(b)*.sup.4                                                                        --  --    0.12                                                                             0.74  0.22                                                                              0.81  Comparative                                                                   Example                            5 M-(b)*.sup.2                                                                       "      --  1.5 × 10.sup.-2                                                               0.12                                                                             0.72  0.20                                                                              0.82  Comparative                                                                   Example                            6 M-(b)*.sup.2                                                                       II-(b)*.sup.4                                                                        --  --    0.12                                                                             0.74  0.21                                                                              0.80  Comparative                                                                   Example                            7 M-37 II(a)*.sup.3                                                                         --  --    0.13                                                                             0.72  0.20                                                                              0.81  Comparative                                                                   Example                            8 M-37 II-(b)*.sup.4                                                                        --  --    0.12                                                                             0.75  0.15                                                                              0.80  Comparative                                                                   Example                            9 M-37 II-7   --  1.5 × 10.sup.-2                                                               0.12                                                                             0.75  0.13                                                                              0.78  Present                                                                       Invention                         10 M-37 II-7   --  0.5 × 10.sup.-2                                                               0.12                                                                             0.76  0.13                                                                              0.78  Present                                                                       Invention                         11 M-37 II-7   --  0.1 × 10.sup.-2                                                               0.12                                                                             0.77  0.13                                                                              0.78  Present                                                                       Invention                         12 M-37 II-7   --  --    0.12                                                                             0.78  0.13                                                                              0.78  Present                                                                       Invention                         13 M-37 II-7    5  --    0.13                                                                             0.79  0.14                                                                              0.80  Present                                                                       Invention                         14 M-37 II-7   10  --    0.13                                                                             0.80  0.14                                                                              0.81  Present                                                                       Invention                         15 M-37 II-7   15  --    0.13                                                                             0.81  0.15                                                                              0.82  Present                                                                       Invention                         16 M-37 II-7   15  1.5 × 10.sup.-2                                                               0.12                                                                             0.78  0.14                                                                              0.80  Present                                                                       Invention                         17 M-37 II-12  --  --    0.12                                                                             0.78  0.13                                                                              0.79  Present                                                                       Invention                         18 M-37 II-22  --  --    0.12                                                                             0.78  0.13                                                                              0.78  Present                                                                       Invention                         19 M-37 II-28  --  --    0.12                                                                             0.79  0.13                                                                              0.79  Present                                                                       Invention                         20 M-37 II-49  --  --    0.12                                                                             0.78  0.13                                                                              0.78  Present                                                                       Invention                         21 M-30 II-7   --  --    0.12                                                                             0.80  0.13                                                                              0.80  Present                                                                       Invention                         22 M-42 II-7   --  --    0.12                                                                             0.79  0.13                                                                              0.79  Present                                                                       Invention                         23 M-43 II-7   --  --    0.12                                                                             0.81  0.13                                                                              0.82  Present                                                                       Invention                         24 M-57 II-7   --  --    0.12                                                                             0.82  0.13                                                                              0.82  Present                                                                       Invention                         25 M-79 II-7   --  --    0.12                                                                             0.80  0.13                                                                              0.81  Present                                                                       Invention                         26 M-81 II-7   --  --    0.12                                                                             0.79  0.13                                                                              0.80  Present                                                                       Invention                         __________________________________________________________________________     *.sup.1 Comparative magenta coupler (M(a)                                     ##STR17##                                                                     *.sup.2 Comparative magenta coupler (M(b))                                    ##STR18##                                                                     -                                                                             *.sup.3 Additive (II(a)) for comparative color developer                      H.sub.2 NOH                                                                   *.sup.4 Additive (II(b)) for comparative color developer                      ##STR19##                                                                     -                                                                        

It is seen from Table 1 that, in the comparative examples, a largeincrease in D_(min) and a large change in gradation are observed withthe aged solutions (Nos. 1 to 6). A large change in D_(min) is observedeven with the couplers of the present invention when color developersoutside the scope of the present invention are used (Nos. 7 and 8).

According to the present invention, photographic properties are lesschanged, and the absence of sodium sulfite and benzyl alcohol providesmore remarkable advantages (comparison of No. 12 with Nos. 9 to 11 andNos. 13 to 16).

EXAMPLE 2

The same experiments as with No. 12 in Example 1 were conducted exceptfor changing the magenta coupler M-37 to M-58, M-70, M-71, M-72 or M-74to obtain preferable results as in Example 1.

EXAMPLE 3

Multi-layer color photographic printing papers having the stratumstructures shown below on a paper support double-laminated withpolyethylene were prepared while changing the magenta coupler. Coatingsolutions were prepared as follows.

Preparation of a coating solution for forming the first layer

27.2 cc of ethyl acetate and 7.7 cc (8.0 g) of a high-boiling solvent(Solv-1) were added to 19.1 g of a yellow coupler (ExY-1) and 4.4 g of acolor image stabilizer (Cpd-1), and the resulting solution wasemulsified and dispersed in 185 cc of a 10% gelatin aqueous solutioncontaining 8 cc of 10% sodium dodecylbenzenesulfonate. This emulsiondispersion was mixed with emulsions EM-7 and EM-8 while controlling thegelatin concentration according to the following formulation to preparea coating solution for forming the first layer. Coating solutions forforming the second to seventh layers were also prepared in the samemanner as with the coating solution for the first layer. As a gelatinhardener for each layer, the sodium salt of1-hydroxy-3,5-dichloro-s-triazine was used.

As a thickening agent, (Cpd-1) was used.

(Stratum structure)

The formulation of each layer is shown below. Numerals represent coatedamounts (g/m²). Amounts of silver halide emulsions are represented asamounts of coated silver.

    ______________________________________                                        Support                                                                       Polyethylene-laminated paper (containing a white                              pigment (TiO.sub.2) and a bluish dye in polyethylene on                       the first layer side)                                                         First layer (blue-sensitive layer)                                            ______________________________________                                        Monodispersed AgClBr emulsion (EM-7)                                                                    0.15                                                spectrally sensitized with sensitizing                                        dye (ExS-1)                                                                   Monodispersed AgClBr emulsion (EM-8)                                                                    0.15                                                spectrally sensitized with sensitizing                                        dye (ExS-1)                                                                   Gelatin                   1.86                                                Yellow coupler (ExY-1)    0.82                                                Color image stabilizer (Cpd-2)                                                                          0.19                                                Solvent (Solv-1)          0.35                                                Second layer (color mixing-preventing layer)                                  ______________________________________                                        Gelatin                   0.99                                                Color mixing-preventing agent (Cpd-3)                                                                   0.08                                                ______________________________________                                        Third layer (Green-sensitive layer)                                           ______________________________________                                        Monodispersed AgClBr emulsion(EM-9)                                                                     0.12                                                spectrally sensitized with sensitizing                                        dyes (ExS-2,3)                                                                Monodispersed AgClBr emulsion(EM-10)                                                                    0.24                                                spectrally sensitized with sensitizing                                        dyes (ExS-2,3)                                                                Gelatin                   1.24                                                Magenta coupler           See TABLE 2.                                        Color image stabilizer (Cpd-4)                                                                          0.25                                                Color image stabilizer (Cpd-5)                                                                          0.12                                                Solvent (Solv-2)          0.25                                                ______________________________________                                        Fourth layer (UV ray-absorbing layer)                                         ______________________________________                                        Gelatin                   1.60                                                UV ray absorbent (Cpd-6/Cpd-7/Cpd-8 =                                                                   0.70                                                3/2/6 by weight)                                                              Color mixing-preventing agent (Cpd-9)                                                                   0.05                                                Solvent (Solv-3)          0.42                                                Fifth layer (Red-sensitive layer)                                             ______________________________________                                        Monodispersed AgClBr emulsion(EM-11)                                                                    0.07                                                spectrally sensitized with sensitizing                                        dyes (ExS-4,5)                                                                Monodispersed AgClBr emulsion (EM-12)                                                                   0.16                                                spectrally sensitized with sensitizing                                        dyes (ExS-4,5)                                                                Gelatin                   0.92                                                Cyan coupler (ExC-1)      1.46                                                Cyan coupler (ExC-2)      1.84                                                Color image stabilizer (Cpd-7/Cpd-8/                                                                    0.17                                                Cpd-10 = 3/4/2 by weight)                                                     Polymer (Cpd-11) for dispersion                                                                         0.14                                                Solvent (Solv-1)          0.20                                                ______________________________________                                        Sixth layer (UV ray-absorbing layer)                                          ______________________________________                                        Gelatin                   0.54                                                UV ray absorbent (Cpd-6/Cpd-8/Cpd-10                                                                    0.21                                                = 1/5/3 by weight)                                                            Solvent (Solv-4)          0.08                                                ______________________________________                                        Seventh layer (Protective layer)                                              ______________________________________                                        Gelatin                   1.33                                                Acryl-modified copolymer of polyvinyl                                                                   0.17                                                alcohol (modification degree: 17%)                                            Liquid paraffin           0.03                                                ______________________________________                                    

Cpd-12 and Cpd-13 were used as irradiation-preventing dyes.

In each layer were further used, as emulsifying and dispersing agents orcoating aids, Alkanol XC (made by duPont), sodium alkylbenzenesulfonate,succinic ester, and Magefacx F-120 (made by Dainippon Ink & Chemicals,Inc.). Further, Cpd-14 and Cpd-15 were used as stabilizers for silverhalides.

Details of the emulsions used are as follows.

    ______________________________________                                                                            Coefficient                                               Grain Size Br Content                                                                             of                                        Emulsion                                                                             Shape    (μm)    (mol %)  Variation*                                ______________________________________                                        EM-7   Cube     1.1        1.0      0.10                                      EM-8   Cube     0.8        1.0      0.10                                      EM-9   Cube     0.45       1.5      0.09                                      EM-10  Cube     0.34       1.5      0.09                                      EM-11  Cube     0.45       1.5      0.09                                      EM-12  Cube     0.34       1.6      0.10                                      ______________________________________                                         ##STR20##                                                                     -                                                                        

Structural formulae of the used compounds are as follows. ##STR21##

Magenta couplers used are as follows.

    ______________________________________                                        Sample A   Magenta coupler M-(a)                                                                          (See Example 1.)                                  Sample B:  Magenta coupler M (b)                                                                          (See Example 1.)                                  Sample C:  Magenta coupler M-37                                               Sample D:  Magenta coupler M-42                                               Sample E:  Magenta coupler M-43                                               Sample F:  Magenta coupler M-57                                               ______________________________________                                    

Running testing was conducted according to the following steps whilechanging the formulation of the color developers. The processing stepswere as follows. Processing amount was 15 m² /day in respectiveprocessings, and the processing was conducted for 30 days.

    ______________________________________                                                                     Replenishing                                                                           Tank                                    Processing steps                                                                          Temp.    Time    Amount*  volume                                  ______________________________________                                        Color development                                                                         35° C.                                                                          45 sec  140 ml   17 liters                               Bleach-fixing                                                                             30-36° C.                                                                       45 sec  215 ml   17 liters                               Stabilizing (1)                                                                           30-37° C.                                                                       20 sec  --       10 liters                               Stabilizing (2)                                                                           30-37° C.                                                                       20 sec  --       10 liters                               Stabilizing (3)                                                                           30-37° C.                                                                       20 sec  200 ml   10 liters                               Drying      70-85° C.                                                                       60 sec                                                   ______________________________________                                         *per m.sup.2 of lightsensitive material                                       (Stabilizing was conducted in a 3tank counter current manner of               stabilizing (3) → (1).)                                           

The formulation of respective processing solutions were as follows.

    ______________________________________                                                            Tank      Replenishing                                    Color developer     Solution  Solution                                        ______________________________________                                        Water               800 ml    800 ml                                          Ethylenediaminetetraacetic acid                                                                   2.0 g     2.0 g                                           5,6-Dihydroxybenzene-1,2,4-tri-                                                                   0.3 g     0.3 g                                           sulfonic acid                                                                 Triethanolamine     8.0 g     8.0 g                                           Sodium chloride     1.4 g     --                                              Potassium carbonate 25 g      25 g                                            N-Ethyl-N-(β-methanesulfonamido-                                                             5.0 g     7.0 g                                           ethyl)-3-methyl-4-aminoaniline                                                sulfate                                                                       Compound B of the present invention                                                               See Table 2.                                              Fluorescent brightening agent                                                                     2.0 g     2.5 g                                           (4,4'-diaminostilbene type)                                                   Water to make       1,000 ml  1,000 ml                                        pH (25° C.)  10.05     10.45                                           ______________________________________                                        Bleach-fixinq solution                                                        (Tank solution and replenishing solution had                                  the same formulation)                                                         ______________________________________                                        Water                     400    ml                                           Ammonium thiosulfate (70%)                                                                              100    ml                                           Sodium sulfite            17     g                                            Iron (III) ammonium ethylenediamine-                                                                    55     g                                            tetraacetate                                                                  Disodium ethylenediaminetetraacetate                                                                    5      g                                            Glacial acetic acid       7      g                                            Water to make             1,000  ml                                           pH (25° C.)        5.6                                                 ______________________________________                                        Stabilizing solution                                                          (Tank solution and replenishing solution had                                  the same formulation)                                                         ______________________________________                                        Formalin (37%)            0.1    g                                            Formalin-sulfurous acid adduct                                                                          0.7    g                                            5-Chloro-2-methyl-4-isothiazolin-3-one                                                                  0.02   g                                            2-Methyl-4-isothiazolin-3-one                                                                           0.01   g                                            Copper sulfate            0.005  g                                            Water to make             1,000  ml                                           pH (25° C.)        4.0                                                 ______________________________________                                    

Running testing (continuous processing) was conducted under eachcondition until the amount of replenishing color developer became threetimes as much as the tank volume (17 liters). Change in stain and in G(green density) of gradation portion were measured at the start and the.end of the running processing using an automatic recording densitometer(type of Fuji Photo Film Co., Ltd.). Further, samples at the end of therunning processing were allowed to stand at 60° C. (5-10% RH) for 4months, and again subjected to measurement of change in G density instained areas.

The following photographic properties of the magenta dyes at the startand the end of the running testing are shown in Table 2.

                                      TABLE 2                                     __________________________________________________________________________           Additive to Color Developer (Compound B)                                      II-(b)*2                                                                      (Comparative II-7         II-12                                               example)     (Present invention)                                                                        (Present Invention)                                          ΔD.sub.min                                                                           ΔD.sub.min                                                                           ΔD.sub.min                               ΔGrada-                                                                      after   ΔGrada-                                                                      after   ΔGrada-                                                                      after                                      ΔD.sub.min                                                                  tion aging                                                                             ΔD.sub.min                                                                  tion aging                                                                             ΔD.sub.min                                                                  tion aging                               Sample (*3)                                                                              (*4) (*5)                                                                              (*3)                                                                              (*4) (*5)                                                                              (*3)                                                                              (*4) (*5)                                __________________________________________________________________________    A*1    +0.03                                                                             +0.6 +0.15                                                                             0 +0.02                                                                           +0.04                                                                              +0.13                                                                             +0.02                                                                             +0.03                                                                              +0.13                               (Comparative                                                                  Example)                                                                      B*1    +0.03                                                                             +0.06                                                                              +0.16                                                                             +0.02                                                                             +0.03                                                                              +0.14                                                                             +0.02                                                                             +0.03                                                                              +0.15                               (B*1)                                                                         C      +0.03                                                                             +0.05                                                                              +0.19                                                                             +0.01                                                                             +0.01                                                                              +0.10                                                                             +0.01                                                                             +0.01                                                                              +0.10                               (Present                                                                      Invention)                                                                    D      +0.03                                                                             +0.06                                                                              +0.18                                                                             +0.01                                                                             +0.01                                                                              +0.10                                                                             +0.01                                                                             +0.01                                                                              +0.10                               (D)                                                                           E      +0.03                                                                             +0.05                                                                              +0.19                                                                             +0.01                                                                             +0.02                                                                              +0.10                                                                             +0.01                                                                             +0.01                                                                              +0.10                               (E)                                                                           F      +0.03                                                                             +0.06                                                                              +0.19                                                                             +0.02                                                                             +0.01                                                                              +0.11                                                                             +0.01                                                                             +0.01                                                                              +0.10                               (F)                                                                           __________________________________________________________________________                        Additive to Color Developer (Compound B)                                      II-22        II-49                                                                     ΔD.sub.min                                                                           ΔD.sub.min                                            ΔGrada-                                                                      after   ΔGrada-                                                                      after                                                   ΔD.sub.min                                                                  tion aging                                                                             ΔD.sub.min                                                                  tion aging                                            Sample (*3)                                                                              (*4) (*5)                                                                              (*3)                                                                              (*4) (*5)                                __________________________________________________________________________                 A*1    +0.02                                                                             +0.04                                                                              +0.14                                                                             +0.02                                                                             +0.04                                                                              +0.14                                            (Comparative                                                                  Example)                                                                      B*1    +0.02                                                                             +0.03                                                                              +0.14                                                                             +0.02                                                                             +0.04                                                                              +0.14                                            (B*1)                                                                         C      +0.01                                                                             +0.01                                                                              +0.10                                                                             +0.01                                                                             +0.01                                                                              +0.10                                            (Present                                                                      Invention)                                                                    D      +0.01                                                                             +0.01                                                                              +0.10                                                                             +0.01                                                                             +0.01                                                                              +0.11                                            (D)                                                                           E      +0.02                                                                             +0.01                                                                              +0.11                                                                             +0.02                                                                             +0.02                                                                              +0.11                                            (E)                                                                           F      +0.01                                                                             +0.01                                                                              +0.11                                                                             +0.02                                                                             +0.01                                                                              +0.11                                            (F)                                                              __________________________________________________________________________     *1 Comparative magenta couplers M(a) and M(b) used in sample A and Sample     B are described in Example 1.                                                 *2 Additive II(b) for comparative color developer is described in Example     1.                                                                            *3 An increase in D.sub.min at the end of running test based on D.sub.min     at the start of running test (stein).                                         *4 An increase in G density of gradation portion at the end of the runnin     based on G density of gradation portion at the start of running.              *5 An increase in D.sub.min of a sample aged at 60° C. for 4 month     based on its D.sub.min at the end of running.                            

Table 2 shows that, in the comparative examples, an increase in D_(min)ΔD_(min)), an increase in gradation (Δgradation) and an increase inD_(min) after agin ΔD_(min) after aging) were very high when II-(b) wasused as the additive (compound B) to the color developer, and that, inthe case of using Sample A or B (containing magenta couplers outside thescope of the present invention),D_(min), gradation and change inΔD_(min) after aging were very high even when color developers of thepresent invention were used.

According to the present invention, the above-described changes inphotographic properties are markedly lowered.

While the present invention has been described in detail and withreference to specific embodiments thereof, it is apparent to one skilledin the art that various changes and modifications can be made thereinwithout departing from the spirit and the scope of the presentinvention.

What is claimed is:
 1. A method for processing a silver halide colorphotographic material containing at least one pyrazoloazole magentacoupler represented by general formula (I), which comprises processingthe light-sensitive material, after imagewise exposure, with a colordeveloper containing an aromatic primary amine color developing agentand at least one member selected from among hydrazines and hydrazidesrepresented by general formula (II): ##STR22## wherein R₁₁ represents ahydrogen atom or a substituent, X represents a hydrogen atom or a groupcapable of being eliminated by a coupling reaction with an oxidationproduct of an aromatic primary amine developing agent, Za, Zb and Zceach represents a methine group, a substituted methine group, ═N-- or--NH--, provided that one of the Za-Zb bond and the Zb-Zc bond is adouble bond and the other is a single bond and, when Zb-Zc is acarbon-to-carbon double bond, it may be a part of an aromatic ring, anda dimer or higher polymer may be formed at Rll or X, or, when Za, Zb orZc represents a substituted methine group, a dimer or higher polymer maybe formed at the substituted methine group; ##STR23## wherein R¹, R² andR³ each independently represents a hydrogen atom, an alkyl group, anaryl group or a heterocyclic group, R4 represents a hydrogen atom, ahydroxy group, a hydrazino group, an alkyl group, an aryl group, aheterocyclic group, an alkoxy group, an aryloxy group, a carbamoyl groupor an amino group, X¹ represents a divalent group, and n represents 0 or1, provided that, when n is 0, R⁴ represents an alkyl group, an arylgroup or a heterocyclic group, and that R³ and R⁴ may together form aheterocyclic ring.
 2. The method for processing the silver halide colorphotographic material as in claim 1, wherein said color developer doesnot substantially contain sulfite ion.
 3. The method for processing thesilver halide color photographic material as in claim 1, wherein saidcolor developer contains 5 ml or less benzyl alcohol.
 4. The method forprocessing the silver halide color photographic material as in claim 1,wherein said pyrazoloazole magenta coupler is selected from the groupconsisting of the couplers represented by general formulae (Ia), (Ib),(Ic), (Id), (Ie), and (If): ##STR24##
 5. The method for processing thesilver halide color photographic material as in claim 1, wherein thesaid hydrazines and hydrazides represented by general formula (II) arepresent in amounts of 0.01 g to 50 g per liter of color developer. 6.The method for processing the silver halide color photographic materialas in claim 2, wherein the content of the sulfite ion is 0 to 0.005 molper liter.
 7. The method for processing the silver halide colorphotographic material as in claim 3, wherein the content of the benzylalcohol is 2 ml or less per liter.
 8. The method for processing thesilver halide color photographic material as in claim 1, wherein thesilver halide emulsion for the light-sensitive material comprises 80 to100 mol % of silver chloride.